CN103391953A - Epoxy resin composition - Google Patents

Epoxy resin composition Download PDF

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Publication number
CN103391953A
CN103391953A CN2011800663729A CN201180066372A CN103391953A CN 103391953 A CN103391953 A CN 103391953A CN 2011800663729 A CN2011800663729 A CN 2011800663729A CN 201180066372 A CN201180066372 A CN 201180066372A CN 103391953 A CN103391953 A CN 103391953A
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composition
epoxy resin
polyisocyanate
compound
hydroxyl
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CN103391953B (en
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C.德比恩
C.埃斯贝林
H.G.G.维贝科
H.维贝科
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Huntsman International LLC
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Huntsman International LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3829—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing ureum groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7825—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing ureum groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Epoxy Resins (AREA)

Abstract

Curable composition obtained by combining and mixing an epoxy resin composition comprising an epoxy resin, a monool and/or polyol and a compound comprising a carboxamide group, and a polyisocyanate composition comprising a polyisocyanate, a lithium halide and a urea compound, wherein the number of moles of lithium halide per isocyanate equivalent ranges of from 0.0001 -0.04 and the number of urea + biuret equivalents per isocyanate equivalent of from 0.0001 -0.4. The epoxy resin composition is claimed as well.

Description

Composition epoxy resin
The curable compositions that the present invention relates to composition epoxy resin and by mixing described composition epoxy resin and polyisocyanate composition, prepare.In addition, the present invention relates to prepare the method for described composition epoxy resin and described curable compositions.The present invention further relates to by making curable compositions react the method for preparing the polyurethane polyureas isocyurnate material, and by making the polyurethane polyureas isocyurnate material of this curable compositions reaction preparation.
Recently proposed to have the curable compositions of the longest 17 hour working life, described composition comprises polymeric polyisocyanate, lithium halide, carbamide compound and epoxy resin, referring to PCT/EP2010/054492.Be used for the carbamide compound of PCT/EP2010/054492 by polymeric polyisocyanate (R 1-NCO) with amine (R 2-NH 2) the reaction preparation, be called carbamide compound, and have following structure R 1– NH-CO-NH-R 2, R wherein 1And R 2Both are not all hydrogen.
We are surprised to find that, contain to comprise by use to have structure-CO-NH 2The composition epoxy resin of compound of formamido-, can towards the longest 300 hours and longer working life the significant prolongation curable compositions working life, and the not curing of negative impact curable compositions subsequently.
Therefore, the present invention relates to a kind of composition epoxy resin, described composition epoxy resin comprises epoxy resin, monohydroxy-alcohol and/or polyvalent alcohol and comprises the compound of formamido-, wherein the hydroxyl equivalent number of every epoxide equivalent is 0.02-100, preferred 0.03-50,0.05-10 most preferably, the methane amide equivalents of every epoxide equivalent is 0.0005-1, preferred 0.005-0.7, most preferably 0.01-0.5.
In addition, the present invention relates to prepare the method for this composition epoxy resin, wherein make monohydroxy-alcohol and/or polyvalent alcohol and the mixture that comprises the compound of formamido-make up with epoxy resin and mix.The relative quantity of selection component, make composition epoxy resin comprise these compositions of the above amount of giving.
The present invention further relates to a kind of by making up and mix the curable compositions of the composition epoxy resin acquisition of polyisocyanate composition and above restriction, described polyisocyanate composition comprises polymeric polyisocyanate, lithium halide and has molecular-weight average and the optional carbamide compound that comprises biuret groups of 500-15000, wherein the mole number of the lithium halide of every isocyanurate equivalent is 0.0001-0.04, the urea of every isocyanurate equivalent+biuret equivalents is 0.0001-0.4, and the epoxide equivalent number of every isocyanurate equivalent is 0.003-1.
The curable compositions that the present invention further relates to by making above restriction prepares the method for polyurethane polyureas isocyurnate material in the rising thermotonus, and the polyurethane polyureas isocyurnate material for preparing in this way.
Finally, the present invention relates to comprise and have structure-CO-NH 2The compound of formamido-be used for extending the purposes of the working life of curable polyisocyanate composition.
Use lithium chloride and the compound that comprises urea groups open in Polymer 45 (2004) 5979-5984 by Sheth, Aneja and Wilkes.The impact of the scope of hydrogen bonding during they have studied the long scope connectivity of reconciling hard segment phase as molecular probe with LiCl in model three segment oligomeric urethanes and have permeated.
In US 5086150, make the reaction under quite the LiCl of a large amount exists of isocyanate-terminated prepolymer and diamines, to prepare the elastomer solution of stablizing at least two days.Start in reaction, the lithium chloride molar weight of every isocyanurate equivalent is quite high, and lithium chloride is as solubilizing agent.Start in reaction, composition is unstable and do not contain urea, in reaction, finishes, and it is elastomerics, is no longer isocyanate composition.The product that obtains is the elastomer solution for the preparation of line and film.
Isocyanic ester and epoxide use and are disclosed in Russian Chemical Reviews 52 (6) 1983,576-593 together with LiCl.Reaction is affected by catalyst property.Generate activated complex under metal halide exists, final De is Dao oxazolidone.One of side reaction is to generate isocyanurate ring, and isocyanurate ring resolves into oxazolidone when with epoxide, processing.Open in addition, epoxide can make the urea bond scission along with Sheng Cheng oxazolidone.
US 4658007 openly contains the method for the polymkeric substance of oxazolidone by polymeric polyisocyanate and polyepoxide reaction preparation bag with organic iodate antimony catalyst.
US 5326833 discloses a kind of composition, and described composition comprises polymeric polyisocyanate, epoxide and by the catalyzer of the solution composition of alkali metal halide in the polyoxy ene compound (for example LiCl).These compositions can be between 0 ℃ and 70 ℃ fast gelation.
Juan etc. are at Journal of East China University of Science and Technology Vol. 32, and No 11,2006, and the impact of LiCl on morphological structure and the character of polyurethane-urea is discussed in 1293-1294.Its demonstration, at first the viscosity of polyurethane-urea solution reduce, and increases subsequently., by making poly-epoxy propylene glycol and isophorone diisocyanate and crossing the quantity gathers isocyanate reaction, can prepare polyurethane-urea.
In US 3517039, by organic diisocyanate and the reaction of organic monocarboxylic acid, preparation acrylated urea-polymeric polyisocyanate.These polymeric polyisocyanates are for the preparation of urethane, while especially in a small amount of branch, catering to the need.
The stabilizing solution of the isocyanuric acid ester-polymeric polyisocyanate that comprises acid amides and/or acyl group urea groups has been described in US 3970600.They avoid depositing thin or coarse crystallization solid in comprising the polymeric polyisocyanate of isocyanurate group.At first make polymeric polyisocyanate and polycarboxylic acid reaction, have the polymeric polyisocyanate of the – acyl group urea groups of acid amides and – replacement with preparation.Then, make this polymeric polyisocyanate trimerizing, to generate isocyanuric acid ester-polymeric polyisocyanate, this conversion is stopped by acid adding.
In JP 2-110123,, in case reached required degree of conversion, just with catalyzer and deactivator, make the aliphatic vulcabond trimerizing, have the polymeric polyisocyanate of isocyanurate structure with preparation.Deactivator has structure-CO-NH 2Or-SO-NH 2, and can be urea, MU, 1,1-dimethyl urea, phenyl carbamate, urethanum or butyl carbamate.Remove subsequently catalyzer, excess diisocyanate and solvent (if use) through deactivating.By using this deactivator, the polymeric polyisocyanate that comprises the poly-isocyanurate structure shows lower variable color degree.
WO 2008/068198 and US 2010/0022707 are open, in case wherein reached required transformation efficiency, just uses deactivator with the method for catalyzer preparation through oligomeric polymeric polyisocyanate, removes subsequently unconverted polymeric polyisocyanate.Deactivator can especially be selected from urea and contain carbamide compound.
The open preparation of EP 585835 comprises the method for the mixture of polyisocyanates of isocyanuric acid ester and carbamate groups, described method comprises makes vulcabond part cyclisation under catalyst for trimerization exists, when reaching required transformation efficiency, catalyst for trimerization is deactivated, make subsequently gained comprise polymeric polyisocyanate and the oxy-compound reaction of isocyanurate group, then isolate monomeric diisocyanate.
Under environment of the present invention, following term has following implication:
1) isocyanate index or nco index or index:
The ratio of the isocyanic ester-hydrogen atoms that exists in NCO-group and batching provides as percentage ratio:
　　 [NCO]?x?100　　　(%).
[active hydrogen]
In other words, in NCO-exponential representation batching the actual isocyanic ester that uses with respect to batching in the percentage ratio of amount of the required isocyanic ester of the isocyanic ester-reactive hydrogen reaction theory of the amount used.
Should observe, isocyanate index used herein should comprise from preparation the actual polymerisation process aspect consideration of the material of isocyanate prepolymer composition and isocyanate-reactive composition.Do not consider to produce any isocyanate group that consumes through modified isocyanate (be included in this area and be called as these isocyanate derivates of prepolymer) or any active hydrogen that consumes in preliminary step (for example, with isocyanate reaction, producing through modified polyalcohol or polyamine) in preliminary step in calculating isocyanate index.Only consider the free isocyanate groups that exists and free isocyanate reactive hydrogen (hydrogen that comprises water, if use) in actual polymerisation stage.
2) refer in this article the sum of the active hydrogen atom that exists with hydroxyl and amido for the expression " isocyanate reactive hydrogen atoms " of calculating the isocyanate index use in response composite; This meaning,, in order to calculate the isocyanate index in actual polymerisation process, think to comprise a reactive hydrogen with a hydroxyl, and a primary amine groups is thought to comprise a reactive hydrogen, and a water molecules is thought to comprise two reactive hydrogen.
3) reactive system: wherein polymeric polyisocyanate separates the combination of the component that remains on one or more containers with the isocyanate-reactive component.
4) number-average's (hydroxyl value of per molecule) of term used herein " average nominal hydroxy functionality " (or abbreviation " functionality ") expression polyvalent alcohol or polyhydric alcohol composition, suppose that this is number-average's (active hydrogen atom number of per molecule) of the initiator of use in its preparation, although in practice because some terminal unsaturations are usually smaller.
5) word " on average " index is equal, except as otherwise noted.
The epoxy resin that uses in composition epoxy resin of the present invention is preferably selected from 20 ℃ of-25 ℃ of any epoxy resin as liquid.
The example of epoxy resin is:
I) poly epihydric alcohol base and poly-(Beta-methyl glycidyl) ester, can obtain with epoxy chloropropane and β methyl epoxy chloropropane reaction respectively by the compound that has two carboxyls in molecule at least.Reacting favourable carries out under alkali exists.
Available aliphatic polycarboxylic acid is as the compound that has at least two carboxyls in molecule.The example of these polycarboxylic acids is oxalic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and dimerization or trimerized linoleic acid.
Yet, also can use alicyclic polycarboxylic acid, for example tetrahydrophthalic acid, 4-methyl tetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthaacid acid.
In addition, can use aromatic polycarboxylic acid, for example phthalic acid, m-phthalic acid or terephthalic acid.
II) poly epihydric alcohol base ether or poly-(Beta-methyl glycidyl) ether, can, by compound and epoxy chloropropane or the β methyl epoxy chloropropane reaction that has at least two free alcohol hydroxyls and/or phenolic hydroxyl group under alkaline condition, perhaps under existing, an acidic catalyst react and obtain with alkaline purification subsequently.
This type glycidyl ether is derived from for example acyclic alcohol, for example derived from ethylene glycol, Diethylene Glycol or more senior poly-(oxygen ethene) glycol, propane-1,2-glycol or poly-(oxypropylene) glycol, propane-1,3-glycol, butane-Isosorbide-5-Nitrae-glycol, poly-(oxygen tetramethylene) glycol, pentane-1,5-glycol, hexane-1,6-glycol, hexane-2,4,6-triol, glycerine, 1,1,1-TriMethylolPropane(TMP), tetramethylolmethane or Sorbitol Powder; And Hydrin.Other glycidyl ether of this type is derived from alicyclic alcohol, as 1,4 cyclohexane dimethanol, two-(4-hydroxy-cyclohexyl) methane or 2,2-pair of (4-hydroxy-cyclohexyl) propane; Perhaps derived from the alcohol that comprises aromatic group and/or other functional group, N for example, N-is two-(2-hydroxyethyl) aniline or p, two (the 2-hydroxyethyl the is amino)-ditans of p'-.
Glycidyl ether also can be based on monokaryon phenol, for example p-tert-butylphenol, Resorcinol or quinhydrones; Perhaps based on multinuclear phenol, two (4-hydroxy phenyl) methane, 4 for example, 4-dihydroxybiphenyl, two (4-hydroxy phenyl) sulfone, 1,1,2,2-four (4-hydroxy phenyl) ethane, 2, two (4-the hydroxy phenyl)-propane or 2 of 2-, two (3,5-, the two bromo-4-hydroxy phenyls) propane of 2-.
For the preparation of other oxy-compound that is fit to of glycidyl ether for by aldehyde (for example formaldehyde, acetaldehyde, trichoro-aldehyde or furtural) with do not replace or by chlorine atom or C 1-C 9The novolak that the phenol that-alkyl replaces or bis-phenol (for example phenol, 4-chlorophenol, 2-methylphenol or 4-TBP) condensation obtain.
III) poly-(N-glycidyl) compound, can be obtained by epoxy chloropropane and the dehydrochlorination reaction of the reaction product of the amine that comprises two amine hydrogen atoms at least.These amine are for example aniline, n-butylamine, two (4-aminophenyl) methane, m-xylene diamine or two (4-methylamino phenyl) methane.
Poly-(N-glycidyl) compound also comprises triglycidyl isocyanurate; The N of cyclic alkylidene urea (for example ethylidene-urea or trimethylene urea), N '-2-glycidyl radical derivative; And the 2-glycidyl radical derivative of glycolylurea (for example, 5,5-T10).
IV) poly-(S-glycidyl) compound, for example derived from two-S-Racemic glycidol radical derivative, two mercaptan such as ethane-1,2-two mercaptan or two-(4-mercapto methyl phenyl) ether of two mercaptan.
V) cycloaliphatic epoxy resin, for example two (2,3-oxirane ring amyl group) ethers, 2,3-oxirane ring amyl group glycidyl ether, 1, two (2, the 3-epoxy cyclopentyloxy) ethane or 3 of 2-, 4-epoxycyclohexyl methyl-3 ', 4 '-epoxy cyclohexane manthanoate.
Also can use wherein 1, the 2-epoxy group(ing) is attached to the epoxy resin of different heteroatomss or functional group, these compounds comprise for example N of PAP, N, O-three-glycidyl radical derivative, salicylic glycidyl ether-glycidyl esters, N-glycidyl-N'-(2-glycidyl oxygen propyl group)-5,5-T10 or 2-glycidyl Oxy-1,3-pair-(5,5-dimethyl-1-glycidyl glycolylurea-3-yl)-propane.
Particularly preferably be those that mention in I and II, those that most preferably mention in II.
The monohydroxy-alcohol that uses in composition epoxy resin of the present invention and/or polyvalent alcohol preferably have the average nominal hydroxy functionality of 1-8 and the molecular-weight average of 32-8000.Also can use the mixture of monohydroxy-alcohol and/or polyvalent alcohol.
The example of these monohydroxy-alcohols is the hydrocarbon monohydroxy-alcohol (for example aliphatic series and polyethers monohydroxy-alcohol) of methyl alcohol, ethanol, propyl alcohol, butanols, phenol, hexalin and the molecular-weight average with 200-5000.the example of polyvalent alcohol is ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, TriMethylolPropane(TMP), Sorbitol Powder, sucrose, glycerine, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, have than these compounds and more many carbon atom and have aromatics and/or the aliphatic polyol of the highest 8000 molecular weight, polyester polyol with molecular-weight average of 200-8000, polyether polyester polyvalent alcohol and the polyether glycol with molecular-weight average of 200-8000 with molecular-weight average of 200-8000.These monohydroxy-alcohols and polyvalent alcohol can be buied.Available example is Daltocel F526, Daltocel F555 and Daltocel F442, is the polyether triol available from Huntsman; Voranol P400 and Alcupol R1610, for respectively available from the polyether glycol of DOW and Repsol; Priplast 1838 and 3196, be the high-molecular-weight poly ester polyol available from Croda; Capa 2043 polyvalent alcohols, available from the straight chain polyester glycol of approximately 400 the average MW of Perstorp; K-flex polyvalent alcohol 188 and A308, be the polyester polyol that has respectively approximately 500 and 430 MW available from King Industries; Aromatic polyester polyols, for example Stepanpol PH56 and BC180, have respectively approximately 2000 and 600 molecular-weight average; , with Neodol 23E, be the aliphatic monohydric alcohol available from Shell.
Most preferably be polyester and the polyether glycol of the average nominal functionality of molecular-weight average with 200-6000 and 2-4.
The compound (also referred to as " methane amide " compound) that comprises formamido-is preferably selected from formula NH 2The compound of-CO-R, wherein R is, 1) hydrogen (H), 2)-NR 1R 2, 3) and have 1-20 carbon atom and the optional alkyl that comprises hydroxyl, ether, halogen and/or amido, or 4)-R 3-CO-NH 2, R wherein 1And R 2Separate, be selected from hydrogen, hydroxyl, halogen and have 1-10 carbon atom and the optional alkyl that comprises hydroxyl, ether, halogen and/or amido, wherein R 3For having the bivalent hydrocarbon radical of maximum 8 carbon atoms.Also can use the mixture of these benzamide compounds.Preferred these methane amides have maximum 499 molecular weight.
Alkyl in these methane amides can be straight or branched, saturated or unsaturated, ring-type or non-annularity, and they can be aliphatic series, aromatics or virtue generation aliphatic series.
Most preferred methane amide is these methane amides, and wherein R is 1)-NR 1R 2, 2) have 1-10 carbon atom and choose the alkyl that comprises 1-3 hydroxyl and/or ether, 3 wantonly) phenyl or 4) tolyl, wherein R 1And R 2Separate, be selected from hydrogen, hydroxyl, phenyl, tolyl and have 1-6 carbon atom and the optional alkyl that comprises hydroxyl and/or ether.These more preferably the mixture of compound be also preferred.
The example of benzamide compound of great use is formula NH 2The compound of-CO-R, the wherein following restriction of R:
Most preferably use urea.It should be noted that, in calculating the methane amide equivalents, urea is thought and comprised 2 formamido-s.
In order to prepare composition epoxy resin of the present invention, above-mentioned benzamide compound and above-mentioned monohydroxy-alcohol and/or polyvalent alcohol are preferably merged and mix in the temperature groups between environmental stress and 10 ℃ and 120 ℃.Although can use the Special Mixed operation, the general mixing enough.If in the rising temperature, mix, can choose wantonly and make the mixture that so obtains cooling, preferably in the temperature between environmental stress and 10 ℃ and 120 ℃, mix with above-mentioned epoxy resin subsequently.The relative quantity of epoxy resin, polyvalent alcohol and benzamide compound is selected in the mode that meets above-mentioned hydroxyl/epoxy group(ing) and methane amide/epoxy group(ing) ratio.
The polymeric polyisocyanate of the polyisocyanate composition that uses for the preparation of the present invention can be selected from aliphatic series and preferred aromatic polyisocyanate.preferred aliphatic polymeric isocyanate is 1, hexamethylene-diisocyanate, isophorone diisocyanate, methylene radical dicyclohexyl vulcabond and cyclohexyl diisocyanate, preferred aromatic polyisocyanate is tolylene diisocyanate, naphthalene diisocyanate, tetramethylxylene diisocyanate, phenylene diisocyanate, the tolidine vulcabond, specifically, methylenediphenyl diisocyanates (MDI) and the polyisocyanate composition that comprises methylenediphenyl diisocyanates are (for example, so-called polymeric MDI, thick MDI, the MDI of uretonimine-modified and the prepolymer with free isocyanate groups of being made by MDI and comprise the polymeric polyisocyanate of MDI) and the mixture of these polymeric polyisocyanates.MDI is most preferred with the polyisocyanate composition that comprises MDI, especially be selected from following: 1) diphenylmethanediisocyanate, comprise at least 35% weight (preferably at least 60% weight) 4,4 '-diphenylmethanediisocyanate (4,4 '-MDI); 2) polymeric polyisocyanate 1) carbodiimide and/or the variant of uretonimine-modified, described variant has 20% weight or larger nco value; 3) polymeric polyisocyanate 1) and/or 2) urethane-modified variant, described variant has 20% weight or larger nco value, and is quantity gathers isocyanate 1) and/or 2) and have the reaction product of the polyvalent alcohol of the average nominal hydroxy functionality of 2-4 and the highest 1000 molecular-weight average; 4) contain and comprise 3 or the diphenylmethanediisocyanate of more polyisocyanate-based homologue; 5) have the prepolymer of 5-30% weight nco value, be any or multiple polymeric polyisocyanate 1)-4) and have the average nominal hydroxy functionality of 2-4 and greater than the reaction product of the polyvalent alcohol of 1000 to the highest 8000 molecular-weight average; With 6) mixture of any above-mentioned polymeric polyisocyanate.
Polymeric polyisocyanate 1) comprise at least 35% weight 4,4 '-MDI.These polymeric polyisocyanates are known in the art, and comprise pure 4,4 '-MDI and 4,4 '-MDI, 2,4 '-MDI and 2, the heterogeneous mixture of 2 '-MDI.It should be noted that, in heterogeneous mixture 2, the amount of 2 '-MDI, definitely at impurity level, generally is no more than 2% weight, and all the other are 4,4 '-MDI and 2,4 '-MDI.These polymeric polyisocyanates are known in the art, and can buy, for example available from the Suprasec of Huntsman RMPR and 1306 (Suprasec be in one or more countries but the Huntsman Corporation of non-All Countries registration or the trade mark of its branch).
Above polymeric polyisocyanate 1) carbodiimide and/or the variant of uretonimine-modified be also known in the art, and can buy, for example available from the Suprasec of Huntsman R2020.Above polymeric polyisocyanate 1) urethane-modified variant is also known in the art, referring to for example The ICI Polyurethanes Book by G. Woods 1990,2 ndEdition, pages 32-3.
Polymeric polyisocyanate 4) also be widely known by the people, and can buy.These polymeric polyisocyanates often are called as thick MDI or polymeric MDI.Example is the Suprasec available from Huntsman R2185, Suprasec R5025 and Suprasec RDNR.
Prepolymer (polymeric polyisocyanate 5)) also be widely known by the people, and can buy.Example is Suprasec R2054 and Suprasec R2061, all available from Huntsman.
Also can use the mixture of above-mentioned polymeric polyisocyanate, referring to for example The ICI Polyurethanes Book by G. Woods 1990,2 ndEdition pages 32-35.These examples that can buy polymeric polyisocyanate are the Suprasec available from Huntsman R2021.
The lithium halide that is used for the polyisocyanate composition of the present invention's use uses with the amount of every isocyanurate equivalent 0.0001-0.04 mole, preferred 0.00015-0.025, and most preferably 0.0005-0.02 mole, be preferably selected from lithium chloride and lithiumbromide.Lithium chloride is most preferred.
The amount of carbamide compound take urea+biuret equivalents as every isocyanurate equivalent 0.0001-0.4 that is used for the polyisocyanate composition of the present invention's use used, preferred 0.001-0.2, most preferably 0.001-0.05.Most preferably in polyisocyanate composition in carbamide compound the urea of every mole of lithium halide+biuret equivalents be 0.5-60, most preferably 0.5-30.Carbamide compound should not comprise other isocyanate-reactive group (that is, the group beyond urea groups).When calculating the urea equivalents, do not consider to have the urea groups in the benzamide compound of maximum 499 molecular weight.
The carbamide compound that is used for the polyisocyanate composition of the present invention's use has the molecular-weight average of 500-15000, preferred 600-10000, most preferably 800-8000.These carbamide compounds are by making polymeric polyisocyanate and amine react to prepare.
Polymeric polyisocyanate for the preparation of these carbamide compounds can be selected from above-mentioned polymeric polyisocyanate.Above-mentioned reference is also applicable at this.Most preferably use polymeric polyisocyanate 1) and 2) and composition thereof.For the preparation of the polymeric polyisocyanate of polyisocyanate composition of the present invention and can be identical or different for the preparation of the polymeric polyisocyanate of carbamide compound.
Amine for the preparation of carbamide compound can be monoamine or polyamine.The preferred use chosen the monoamine that comprises a small amount of polyamine wantonly.The average amine functionality of these mixtures is preferably maximum 1.2.Most preferably only use monoamine.These amine are preferably primary amine.
In a single day the molecular weight of amine to react with the polymeric polyisocyanate of selecting, and the molecular weight of the carbamide compound that obtains is selected with regard to the mode that drops in above scope.The molecular weight of general amine is 200-7500, preferred 200-4500, most preferably 200-3000.
The optional leisure of amine those amine known in the art, for example hydrocarbon of amine end-blocking, polyester, polyethers, polycaprolactone, polycarbonate, polymeric amide and composition thereof.Most preferably the polyoxyalkylene monoamine of amine end-blocking, more particularly, the polyoxyethylene polyoxypropylene monoamine.Oxypropylene content in preferred these polyoxyalkylene monoamines is in gross weight at least 50% weight of monoamine molecule, preferably at least 75% weight.Preferred polyoxyalkylene monoamine has monoalkyl at the other end of polymer chain, and alkyl has 1-8 carbon atom, preferred 1-4 carbon atom.These monoamines are known in the art.They are by making the alkyl single methanol alkoxylate with 1-8 carbon atom, and by making subsequently the polyoxyalkylene monohydroxy-alcohol change into monoamine, prepare.These monoamines can be buied.Example is Jeffamine RM-600 and M-2005, both are all available from Huntsman (Jeffamine is at the Huntsman Corporation of one or more but non-All Countries registration or the trade mark of its branch).Also can use the mixture of monoamine.
In view of above-mentioned, the most preferably carbamide compound that is used for the polyisocyanate composition that the present invention uses is for by making methylenediphenyl diisocyanates or comprising polymeric polyisocyanate or the mixture of these polymeric polyisocyanates and the carbamide compound that the reaction of polyoxyalkylene monoamine obtains of methylenediphenyl diisocyanates, described polyoxyalkylene monoamine comprises the oxypropylene group by the amount of monoamine molecule total weight at least 75% weight, and the molecular-weight average with 200-3000, wherein amine is primary amine.
Polymeric polyisocyanate and monoamine are made up and mix, and make their reactions.Exothermic heat of reaction, therefore, do not need heating and/or catalysis, although can heat and/or catalysis, if think convenient.For example, polymeric polyisocyanate and/or monoamine are preheating to 40-60 ℃, and with their mixing, may are easily.After mixing,, for fear of side reaction, for example, generate biuret, the temperature of reaction mixture preferably remains on lower than 90 ℃.In order to guarantee all amine reactions, can use slightly excessive polymeric polyisocyanate, therefore, preferably the index with 101-110 reacts.After maximum 1 hour, can think and react completely, carbamide compound can be used for preparing the polyisocyanate composition that the present invention uses at any time.
Owing to using a small amount of excessive polymeric polyisocyanate in preparing carbamide compound, and due to carbamide compound is added to relatively a large amount of polymeric polyisocyanates at next step, some urea groups may change into biuret groups., by controlling temperature of reaction and the temperature of mixing step subsequently, can avoid as far as possible these biurets generations.Generally change into the urea groups number of biuret groups less than 25%, preferably less than 10%.
Polyisocyanate composition used according to the invention is by mixing polymeric polyisocyanate, carbamide compound and lithium halide to prepare in envrionment conditions or in rising temperature (for example, at 40-70 ℃) with any order.Preferably, with lithium halide and carbamide compound premix, subsequently this mixture is added to polymeric polyisocyanate, and mixes.Before mixing lithium halide and carbamide compound, making lithium halide be dissolved in solvent may facilitate, and for example organic solvent, for example pure, as methyl alcohol or ethanol.The lithium halide that then will dissolve is added to carbamide compound.Subsequently, if necessary, can slough solvent.Premix is blended in envrionment conditions or in rising temperature (for example, at 40-70 ℃), carries out, and by normal stirring, is undertaken.The mode of the relative quantity of isocyanate group, urea groups and lithium halide that the relative quantity of polymeric polyisocyanate, carbamide compound and lithium halide has been described before having with final polyisocyanate composition used according to the invention is selected.Be not bound by any theory, believe that lithium halide exists with solubilized form, with urea groups as the complexing of so-called bidentate complex compound.
Polyisocyanate composition is used for preparing curable compositions of the present invention by the epoxide equivalent number take every isocyanurate equivalent as the relative quantity combination of 0.003-1 (preferred 0.003-0.5, most preferably 0.005-0.25) and blending epoxy composition and polyisocyanate composition.These compositions preferably merge and mix in set of environmental conditions.The relative quantity of composition to be to provide the mode of the index of 300-100000 to select to curable compositions, preferred 500-10000.
The curable compositions that so obtains has satisfactory stability under envrionment conditions.It is used for by allowing to prepare the polyurethane polyureas isocyurnate material in the rising thermotonus.Therefore, the invention further relates to by making the polyurethane polyureas isocyurnate material of curable compositions of the present invention in the preparation of rising thermotonus, with can be by the polyurethane polyureas isocyurnate material that curable compositions of the present invention is obtained in the rising thermotonus, with by making curable compositions of the present invention prepare the method for these polyurethane polyureas isocyurnate materials in the rising thermotonus.Preferred reaction is carried out with the index of 300-100000, most preferably 500-10000.Preferred heating, so that curable compositions reaches the temperature higher than 50 ℃, preferably higher than 80 ℃.Then, but curable compositions fast setting (so-called fast curing), simultaneous temperature further raise (exothermic heat of reaction).
Before making its curing, curable compositions can be sent in mould, to give its definite shape, perhaps send in the cavity of object, to provide the polyurethane polyureas isocyanuric acid ester inner to object, perhaps deliver on surface, this surface is provided polyurethane polyureas isocyanuric acid ester tectum, perhaps,, by it being applied to the interior and/or outside surface of object or pipe, can be used for repairing object, particularly pipe (example of these tubing patch has been described in US 4009063,4366012 and 4622196), perhaps can be used for making material bonding, be disclosed in WO 2007/096216.
Before curable compositions is solidified, additive can be joined wherein or its component in.The example of additive be other catalyzer, whipping agent, tensio-active agent, water scavenging agent (for example, alkyl orthoformate, specifically, orthoformic acid three isopropyl esters), biocide, fire retardant, smoke suppressant, UV stablizer, tinting material, softening agent, inner pattern releasing agent applicable, rheology modifier, wetting agent, dispersion agent and weighting agent.
If necessary, can make polyurethane polyureas isocyurnate material of the present invention through after fixing.
The present invention is with following embodiment explanation.
Embodiment
Chemical used:
Jeffamine M-600: multifunctional polyoxy ethene polyoxypropylene primary amine has approximately 560 molecular weight and about 9/1 oxypropylene/oxygen ethylene ratio.Derive from Huntsman.In these embodiments, be called M-600.
Suprasec 1306 polymeric polyisocyanates, available from Huntsman:4,4 '-MDI.In these embodiments, be called S1306.
Suprasec 2020 polymeric polyisocyanates: the polymeric polyisocyanate of uretonimine-modified, available from Huntsman, is expressed as S2020 in these embodiments.
Alcupol R1610 polyvalent alcohol,, available from Repsol, be expressed as R1610 in this article, has the approximately polyoxypropylene triol of 1050 molecular-weight average.
Daltocel F526 is polyoxyethylene triol, and available from Huntsman, MW approximately 1300.Daltocel is the trade mark of Huntsman Corporation company or its branch, in one or more but non-All Countries registration.Daltocel F442 and Daltocel F55 are also polyether glycols,, available from Huntsman, have 3 nominal functionality, have respectively approximately 4000 and 6000 molecular-weight average.
Voranol P400: available from the polyvalent alcohol of DOW, a kind of polyoxypropylene diols that has approximately 430 molecular-weight average.
Carbalink HPC: the carboxylamine hydroxypropyl acrylate, available from the benzamide compound of Huntsman.
Araldite DY-T epoxide, available from Huntsman, the triglycidyl group ether of TriMethylolPropane(TMP), be expressed as DY-T in this article.Araldite and Carbalink are the trade marks of Huntsman Corporation company or its branch, in one or more but non-All Countries registration.
All do not observe the generation biuret in following examples.
Embodiment 1
Preparation comprises the polyisocyanate composition of lithium chloride and carbamide compound
To make its reaction 1 hour at some mole number amine of 50 ℃ of maintenances with also in some mole number polymeric polyisocyanates 1 mixing of 50 ℃ of maintenances, stir simultaneously, to generate carbamide compound.Temperature of reaction remains on 80 ℃.Make a certain amount of salt be dissolved in a certain amount of ethanol, stir simultaneously.
This solution is added to the carbamide compound of the above preparation that still remains on 80 ℃.Continued stir about 15 minutes.By 85-95 ℃ of distillation, sloughing a great deal of ethanol.Provide in following table 1 together with the amount of the amount of the urea/salt mixture that so obtains and amine, polymeric polyisocyanate 1 and used salt and the amount of type and ethanol used.
Urea/the salt mixture of a certain amount of preparation like this (having approximately 60 ℃ of temperature) is joined certain polymeric polyisocyanate 2, and mix, with the polyisocyanate composition for the preparation of with the composition epoxy resin use.
In following table 2, provide together with the ratio of the amount of composition used and type and urea+biuret equivalents/isocyanurate equivalent and salt mole number/isocyanurate equivalent and urea+biuret equivalents/salt mole number.Weight part is expressed as pbw.
Table 1
Carbamide compound Amine type/amount, mole Polymeric polyisocyanate 1 type/amount, mole Salt type/amount, gram Ethanol/amount, gram Urea+salt mixture/amount, gram
A M-600/2 S1306/1.04 LiCl/23.9 125.3 1407.6
B M600/2 S1306/1.04 LiCl/100.7 528.5 1484.4
C M-600/2 S1306/1.04 LiCl/48.6 255.0 1432.3
D M-600/2 S1306/1.04 LiCl/11.8 62.1 1396.0
Table 2
Mixture of polyisocyanates Carbamide compound, from table 1/ amount, pbw Polymeric polyisocyanate 2 type/amounts, pbw Urea+biuret/NCO ratio Salt/NCO ratio Urea+biuret/salt ratio
1 A/5 S2020/95 0.0109 0.003 3.65
2 B/1.25 S2020/95 0.0027 0.003 0.91
3 C/2.5 S2020/95 0.0055 0.003 1.82
4 A/2.5 S2020/95 0.0055 0.0015 3.65
5 A/15 S2020/95 0.0328 0.009 3.65
6 A/1.25 S2020/95 0.0027 0.0007 3.65
7 D/10 S2020/95 0.0219 0.003 7.30
The preparation of composition epoxy resin of the present invention
Benzamide compound is added to polyvalent alcohol 1, and environmental stress and 120 ℃, stirred 1 hour., if use the second polyvalent alcohol, add polyvalent alcohol 2.After making this mixture be cooled to envrionment conditions, add Araldite DY-T, and stir under envrionment conditions.Amount and the type of composition used provide in table 3, wherein also show the equivalence ratio of OH/ epoxy group(ing) and methane amide/epoxy group(ing).
The preparation of curable compositions of the present invention and poly-isocyanurate material
The composition of table 2 was mixed 30 seconds with composition epoxy resin of the present invention (with comparative composition), and in room temperature, place, with the thermopair of placing according to utilization, to the temperature distribution that temperature starts to rise, determine working life in liquid resin.Make the curable compositions reaction, to prepare polyurethane polyureas isocyurnate material of the present invention.The existence of isocyanurate group is proved by Fourier transform infrared spectroscopy (FTIRS).
Epoxide equivalent number and the working life of composition used, amount (weight part), every isocyanurate equivalent provide in table 3.
In the 1st row, A1 refers to use carbamide compound A (table 1) and mixture of polyisocyanates 1 (table 2), and A6 refers to use carbamide compound A and mixture of polyisocyanates 6., for B2, with carbamide compound B and mixture of polyisocyanates 2, carry out 9 different tests.
Table 3
Table 3(is continuous)
Figure 2011800663729100002DEST_PATH_IMAGE006
Other embodiments of the invention
Provided the information that relates to several other tests in table 4, be similar to table 3, difference is to provide the T of poly-isocyanurate g, rather than the working life of curable compositions.By to having the approximately sample of 4mm thickness, carrying out differential mechanics heat analysis mensuration T g, sample solidified 1 hour at 125 ℃ in baking oven at the open type mould.Utilize other after fixing, T gMay be higher.
Table 4
Figure 2011800663729100002DEST_PATH_IMAGE008
。

Claims (16)

1. composition epoxy resin, described composition epoxy resin comprise epoxy resin, monohydroxy-alcohol and/or polyvalent alcohol and comprise and have structure-CO-NH 2The benzamide compound of formamido-, wherein the hydroxyl equivalent number of every epoxide equivalent is 0.02-100, preferred 0.03-50,0.05-10 most preferably, the methane amide equivalents of every epoxide equivalent is 0.0005-1, preferred 0.005-0.7, most preferably 0.01-0.5.
2. the composition of claim 1, wherein monohydroxy-alcohol and/or polyvalent alcohol have the average nominal functionality of 1-8 and the molecular-weight average of 32-8000, and wherein the hydroxyl equivalent number of every epoxide equivalent is 0.05-10.
3. the composition of claim 1 to 2, wherein benzamide compound has structure NH 2-CO-R, wherein R is, 1) hydrogen (H), 2)-NR 1R 2, 3) and have 1-20 carbon atom and the optional alkyl that comprises hydroxyl, ether, halogen and/or amido, or 4)-R 3-CO-NH 2, R wherein 1And R 2Separate, be selected from hydrogen, hydroxyl, halogen and have 1-10 carbon atom and the optional alkyl that comprises hydroxyl, ether, halogen and/or amido, wherein R 3For having the bivalent hydrocarbon radical of maximum 8 carbon atoms, and the mixture of these compounds, wherein the methane amide equivalents of every epoxide equivalent is 0.01-0.5.
4. the composition of claims 1 to 3, wherein benzamide compound has structure NH 2-CO-R, wherein R is 1) – NR 1R 2, 2) have 1-10 carbon atom and choose the alkyl that comprises 1-3 hydroxyl and/or ether, 3 wantonly) phenyl or 4) tolyl, wherein R 1And R 2Separate, be selected from hydrogen, hydroxyl, phenyl, tolyl and have 1-6 carbon atom and the optional alkyl that comprises hydroxyl and/or ether, and the mixture of these compounds.
5. a method for preparing the composition of claim 1-4, wherein make the mixture of polyvalent alcohol and benzamide compound make up with epoxy resin and mix.
6. one kind by make up and mixes the curable compositions of the composition epoxy resin acquisition of polyisocyanate composition and claim 1-4, described polyisocyanate composition comprises polymeric polyisocyanate, lithium halide and has molecular-weight average and the optional carbamide compound that comprises biuret groups of 500-15000, wherein the mole number of the lithium halide of every isocyanurate equivalent is 0.0001-0.04, the urea of every isocyanurate equivalent+biuret equivalents is 0.0001-0.4, and the epoxide equivalent number of every isocyanurate equivalent is 0.003-1.
7. the composition of claim 6, wherein carbamide compound does not comprise urea groups other isocyanate-reactive group in addition, wherein the urea of every isocyanurate equivalent+biuret equivalents is 0.001-0.2, wherein carbamide compound is by making methylenediphenyl diisocyanates or comprising the polymeric polyisocyanate of methylenediphenyl diisocyanates or the mixture of these polymeric polyisocyanates and polyoxyalkylene monoamine reaction preparation, described polyoxyalkylene monoamine comprises the oxypropylene group by the amount of monoamine molecule total weight at least 50% weight, and the molecular-weight average with 200-3000, wherein amine is primary amine, wherein the urea of every mole of lithium halide+biuret equivalents is 0.5-60.
8. the composition of claim 6 to 7, wherein polymeric polyisocyanate is methylenediphenyl diisocyanates or comprises the polyisocyanate composition of methylenediphenyl diisocyanates or the mixture of these polymeric polyisocyanates.
9. the composition of claim 6 to 8, wherein the amount of lithium halide is 0.00015-0.025 mole/isocyanurate equivalent.
10. the composition of claim 6 to 9, wherein lithium halide is lithium chloride.
11. the composition of claim 6 to 10, wherein epoxy resin is liquid at 20-25 ℃.
12. method for preparing the curable compositions of claim 6 to 11, described method comprises makes polyisocyanate composition claimed in claim 6 and composition epoxy resin claimed in claim 6 make up and mix, and it is 0.003-1 that the amount of composition epoxy resin should make the epoxide equivalent number of every isocyanurate equivalent.
13. a polyurethane polyureas isocyurnate material, described material prepares in the rising thermotonus by the curable compositions that makes claim 6 to 11.
14. a polyurethane polyureas isocyurnate material, described material can obtain in the rising thermotonus by the curable compositions that makes claim 6 to 11.
15. a method for preparing the polyurethane polyureas isocyurnate material of claim 13 to 14, described method comprise that the curable compositions that makes claim 6 to 11 is in the rising thermotonus.
16. comprise and have structure-CO-NH 2The compound of formamido-be used for extending the purposes of the working life of curable polyisocyanate composition.
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